Patent GB-855238-A (GB)
Title: Insecticidal organic phosphates
IPC: C07F9/113
Filed: 1958-12-22
Abstract: The invention comprises triesters of the acid of the formula: (HO)2P(O) O C(CH3) = CH COOH wherein the total number of carbon atoms in the three ester groups is at least eight, the carboxyl group being esterified with a monohydric compound or with a mono-ester or mono-ether of a dihydric compound, said monohydric or dihydric compound containing at least one benzene nucleus in the molecule and the hydroxy groups attached to phosphorus being esterified with an aliphatic hydroxy compound preferably with a lower aliphatic alcohol containing 1 to 4 carbon atoms, especially methyl or ethyl alcohol. Preferred triesters are those in which the carboxy group is esterified with a phenol or aromatic alcohol which may be unsubstituted or substituted in the benzene nucleus by at least one halogen atom, e.g. chlorine, or by one ether or ester group.  The products may be obtained by reacting a triester of phosphorous acid at elevated temperature with an ester derived from alphachloroacetoacetic acid and a monohydric compound or a mono-ester or mono-ether of a dihydric compound, said monohydric or dihydric compound containing at least one benzene nucleus in the molecule, a molecule of an organic chloride corresponding to the ester group in the triphosphite being split off in the reaction.  If the three ester groups in the triphosphite are different the smallest group splits off, thus if diethyl 2-methoxyethyl phosphite is used ethyl chloride is split off and the 2-methoxy-ethyloxy group remains attached to the phosphorus atom.  Examples are given for the production of triesters of the above formula in which the two hydroxy groups attached to the phosphorus atom are esterified with methanol and which the carboxylic ester residue is 2-(p-chlorophenoxycarbonyl)-, 2-(p-chlorobenzyloxycarbonyl), 2-(o-chlorobenzyloxycarbonyl)-, 2-(2,4-dichlorobenzyloxycarbonyl)-, 2-(3,4-dichlorobenzyloxycarbonyl), 2-(p-chloro-alphamethylbenzyloxycarbonyl)-, 2-(2,3,4,5,6-pentachlorobenzyloxycarbonyl)-, 2-phenoxycarbonyl-, 2-benzyloxycarbonyl-, 2-(p-methoxyphenoxycarbonyl)-, 2-(p-tolyloxycarbonyl)-, 2-(2-phenylethoxy)carbonyl-, 2-(p-methoxybenzyloxycarbonyl)-, and 2-(alphamethylbenzyloxycarbonyl)-, respectively.  The products are useful as insecticides (see Group VI).  The alpha-chloroacetoacetates used as starting materials may be obtained by reacting the corresponding unchlorinated acetoacetates with SO2Cl2 and the preparation of the 0-chlorobenzyl-, 2,4-dichlorobenzyl-, p-chloro-alpha-methylbenzyland alpha-methylbenzyl-alpha-chloroacetoacetates is described. Specification 807,119 is referred to.ALSO:An insecticidal composition comprises as active ingredient or ingredients one or more triesters of an acid of the formula:  <FORM:0855238/VI/1> wherein the total number of carbon atoms in the ester groups is at least eight, the carboxyl group being esterified with a monohydric compound or with a mono-ester or mono-ether of a dihydric compound, said monohydric or dihydric compound containing at least one benzene nucleus in the molecule and the hydroxy groups attached to phosphorus being esterified with an aliphatic hydroxy compound, especially methanol or ethanol (see Group IV(b)).  The active ingredient may be used with a surface active agent or with a carrier or both.  The carrier may be solid or liquid and other insecticides may also be present, e.g. pyrethrum, rotenone, sabadilla, DDT, benzene hexachloride, aldrin, dieldrin, endrin, thio-diphenylamine, cyanides, tetraethyl pyrophosphate, diethyl-p-nitrophenyl thiophosphate, azobenzene, and compounds of arsenic, lead and/or fluorine.  Specified diluents and adjuvants are acetone, kerosene and other light mineral oil distillates, talc, bentonite, lime, gypsum, pyrophyllite, fatty acid soaps, resin salts, saponins, gelatin, casein, long chain fatty alcohols, alkyl aryl sulphonates, long chain sulphonates, phenolethylene oxide condensates, C12 to C20 aliphatic amines and ammonium salts.  Several triesters are specified, typical products being those of the above formula in which the two hydroxyl groups p are esterified by methanol and the carboxylic ester group is 2-(p-chlorophenoxycarbonyl)-, 2-phenoxycarbonyl, 2-benzyloxycarbonyl-, and 2-(2, 3, 4, 5, 6-pentachlorobenzyloxycarbonyl) respectively.  Specification 807,119 is referred to.